Treatment of cellulose acetate



Patented Dec. 11, 1928..

UNITED STATES I PATENT OFFICE.

GEORGE HOLLAND ELLIS, OF SPONDON, NEAR DERBY, ENGLAND, ASSIGNOB TO CEL- ANESE CORPORATION OF AMERICA, A CQRPORATION OF DELAWARE.

'J. REA'.III\1'EN"JI OF GELLULOSE ACETATE.

1'0 Drawing. Application filed August 15, 1925, Serial No. 50,525, anfi in Great Britain September 19,

This invention relates to dyeing, printing 'or stencilling (all hereinafter in the claims hereinafter in the claims included in the term materialscomprising cellulose acetate.

- described processes for dyeing, printing or stencilling the goods of or containing cellulose acetate by colouring matters or organic compounds having affinity for'cellulose acetate or capable of colouring thesame, but ,which are insoluble or practlcally insoluble in Water or are of relatively low solubility in Water, 'said colouring matters or organic compounds being employedin the form of I soluble or more soluble modifications obtained by treating them prior to addition to the dyebaths or preparations for printing and the like, with bodies having oily or fatty characteristics, namely higher fatty acids or sul- I phated or other derivatives thereof containing salt-forming groups, e. g. the sulpho group, carboxyl group or salts of such acids or derivatives.

According to the present invention I employ for the dyeing, printing or stencilling of cellulose acetate or goods contaming the same any insoluble or relatively mso-luble colouring matters or compounds havingaffimitv for cellulose acetate or capable of dyeing tliessame all of which are hereinafter in the claims included in the expression relatively Water-insoluble organic compounds capable of coloring cellulose acetate, in the form ofsoluble or more soluble modificatio'nsp'repared by pretreatment with s olubihz1ng agents consisting of or comprislng one or .more bodies being T Witchell reagents, which expression includes sulphoaromatic .fatty acids, such as sulphobenzene steanc acid,

As before stated any insoluble or relatively insoluble colouringmatter or compound having affinity for .cellul ose acetate or capable of coloring the same may be used for the present invention. Thus for example I may employ insoluble or relatively insoluble colouring matters or compounds more particularly specified in the previous U. S. application Serial No. 664,780, Patent No. 1,618,413, for instance, non-sulphonated or other insoluble or relatively insoluble derivatives of the azo class, simple amino bases, .unreduced indophe nols (aryl or substituted aryl benzo-naphtho quinonemonoimides) or insoluble or relatively' insoluble colouringmatters of the fol- 1 Inmy U. S. Patent No. 1,618,413, there 1s 1 owing classes: polyphenyl methane, oxazine,

azine, thiazine, unre'duced indigoid or basic I lone compounds such as are specified in the previous U. S. application Serial No. 737,903,

filed, 15 September, 1924 Patent No. 1,600,277.

Or, for example, I may employ the insoluble or relatively insoluble colouring matters specified in'the previous U. S. application Serial No. 740,413, filed 27 September, 1924, *Patent No. 1,641,965, i. e. vat dyestuffs of the anthraquinone series in the unreduced state, for example indanthrene, cibanone, 'algol, helindone or other vat dyestuffs of the anthraquinone series in the unreduced state.

Qr, for example, I may employ insoluble or relatively insoluble nitro derivatives of ,diarylamine such as are specified in U. S, application S. No. 6,460, filed 2 February, 1925 Patent No. 1,618,415.

It is to be understood that any other insolu-v ble or relatively insoluble colouring matter or compound having aflinity for cellulose acetate or capable or colouring the same may be used for the process of the present invention. The insoluble or relatively insoluble colour, ing matters or compounds for use in the pres ent invention will usually contain no strongly acidic groups such as the sulpho group and when basic colouring matters or compounds are employed they are always used in form of the base and not in the form of salts such as the hydrochloride or other such salt.

The solubilization of the aforesaid insoluble or relatively insoluble colouring matters or compounds may be effected by mixing or grinding them with one or more of the solubilizingc-agents of the present invention, in

presenceor absence of water and heating it necessary, the solubilized modifications being otherwise colouring the goods containing 1 agents of the present .invention and the dye to form a further dyestuif or dyestuifs.

When dyeings or colourings-are to be produced by theazoic process (i. e. wherein the actual 'dyestufis are produced on the material by coupling of simpleamino bases with developers on the material) the insoluble or relatively insoluble component (whether base or developer) maybe solubilized with the ing or developing conducted as usual.

' With reference to dyeing or coloring by means of the azoic process, wherein the actual dyestuffs are produced on the cellulose acetate fibre or material by the coupling of simple amino bases with developers, it ismnderstdod -that the expression organic compounds cap-able of coloringcellulose acetate employed in the claims appliesto said bases or developers in the sense that they are capable of coloring the "cellulose acetate by such production of a dye thereon, whether or not the bases or-developers-themselves color cellulose acetate.

Other colouring matters which are not deleteriouslyaffected by the'solubilizing agents of the present invention may, if desired, be.

dyed on the material together with the colouring matters or compounds of the character before indicated. 1

Mixed goods may be dyed or otherwise coloured in uniform or contrasting effects with or without employment of other dyestufl's or components'according to the character of the non-acetate portion of the goods, said other dyestuifs or components being applied if desired before or after-the application of the hereinbefore specified insoluble or relatively insoluble dyestuffs *or compounds or when. not deleteriously affected thereby they may be applied in conjunction therewith.

The solubilizing agents employed accords in to the present invention as hereinbefore re erred to, may be prepared in any known or suitable way. "The following examples A.

and B. may conveniently begiyen to illustrate methods by which sulpho aromatic fatty acid solubilizing agents such as referred to may be; prepared, itbeing of course understood that I in no way limit myself to the use of solubilizing a ents so prepared and that I may use any at er solubilizing agents hereinbefore indicated.

A. 25 kilogs. of naphthalene are mixed with 25' kilogs. of oleic acid by warming to 80 C. The mass is then cooled quickly and the resultant paste is added slowly to 100 made alkaline with :requisite quantities When the addition is complete the temperature is-raised very gradually to 100 C. at which it is maintained for 3 hours. Care is needed during this heating to prevent afrothing. After cooling, the mixture is poured into 250 litres of water and treated with 50 kilogsk of common salt. The. whole is allowed to separate, when the top aqueous layer is decanted off leaving an oily product which is washed several times with 20% brine. The product is then suitable for use for solubilization or dispersion of colouring matters or dyestuds in accordance with the present invention. Where desired it may be neutralized o;

caustic soda.

kilogs. of 20% oleum with vigorousagitation, I {the temperature being kept below 40 C.

B. The process described in'A. is repeated exactly but substituting the naphthalene by an equal 'weight of benzene. Owing to the lower boiling point of the latter theoperation of heating is done under reflux, working up, on the same lines as in A.

. The following examples will serve to illustrate how theinvention may be carried out, it being understood that they are in no way limitative andmay be varied widely.

Example 1.

diphenylamine 25% aqueouspaste are finely ground and 3-4 kilogs. of the sulpho-aromatic fatty acid product prepared according to A. are added, the whole being well stirred. The mixture is heated until the maximum degree of dispersion is achieved and then diluted with boiling waterand passed through a sieve into a suitable dyeing machine or vat containin g water acidified with 2 litres of formic acid 80%. The goods are entered and the temperature raised according to the common methods of dyeing until the shade is achieved.

Ewamp'le 2.

To dye a shade of reddish blue on 25 kilogs. of-cellulose acetate woven fabric, 2 'kilogs. of"

25% aqueous paste of dimethyl-para-amino- 11 5 phenyl-1: i-naphthoquinone-monoimide are mixed with 2 kilogs of a sulphoaromatic fatty acid in the form of its sodium salt prepared according to A. above, and the wholeis eated to obtain good dispersion. 'The'resultant mass is diluted with boiling water and added through a sieve to a suitable machine'such as a dye jigger containing soft water. The goods are entered. and passed through repeatedly in the manner common with this machine. The goods are then rinsed, dried and finished as is requisite.

E trample To dye a brilliant scarlet red shade by the azobenzene The goods are entere v in B. above.

} aminotriphenylcarbinol azoic process on 100 kilogs. of cellulose acetate fabric,

base is treated with 4 kilogs. of a sulphoaromatic fatty acid preparation, made according to A. The mass is stirred and heated until the maximum dispersion is obtained when it is well diluted with boiling water and the preparation added through a sieve to a suitable dyeing machine for example of the winch or reel type containing a sufiiciency of water acidulated with 4 litres of acetic acid 40%. The temperature is raised until the bath is as well exhausted as required. The goodsare rinsed and then the base di'azotized with sodium nitrite and hydrochloric acid and again rinsed and developed with sodium betanaphtholate"according to procedures .well known in the art.

Example 4.

blue on 100 kilogs. of cellulose acetate woven I fabric, 10 kilogs, of 1-monomethyl-amino-4- paratolylamino-anthraquinone 25% aqueous paste are treated with 10 kilogs. of a sulphoaromatic acid preparation made as described The mass, after being well mixed is heated to obtain the maximum degree of dispersion possible, and then diluted I with boiling water and added to water contained in the beck of a jig type of machine. The rolled up goods are entered in the usual manner when dyeing on this type of machine and passed through continuously with raising of temperature until the desired shade has been obtained, when rinsing and any after-treatment or finishing in common practice may follow. p

E'ammple 5.

- To dye a brilliant bluish green on 100 kilogs. of cellulose acetate yarns in the form of hanks, 2 kilogs. of tetrarnethyldipara- (malachite green base) are finely ground and mixed with 8 kilogs. of sulpho aromatic fatty acid prepared according to B. above. The mass is heated to obtain the maximum degree of dispersion and then diluted with boiling water and added through a sieve to adye-bath containing a'sufliciency water, say 3,000 litres at a temperature of C. and worked in a suitable manner, the temperature being raised until the maximum degree of exhaustion is obtained. A Warm rinse with water acidified with acetic or formic acid preferably follows, afterwards further .rinsing, drying and finishing as desired. 7

Eat-ample 6.

depth of shade.

6 equal proportions ofthe two fibres, 6 lbs. of a 1 kilog. of finely ground amido- 25 0 aqueous paste of 4-chlor-2-nitrophenyl- 4tolylamine are well ground to obtain maximum dispersion. Boiling water is then added and the hot liquid then passed through a sieve into a suitable dyeing machine such as winch or reel. type commonly employed containing 5,000 litres of water acidified With 4 kilogs. of formic acid 90%. To the above dye bath is then added a solution of 2 kilogs. of the diamino-anthrarufinand treated with 6 ,kilogs. of sulphoaromatic fatty acid p'repared'according to A and the mass heated 'disulphonic aciddyestuff knownas. Alizarin Y Delphinol B. in a sufficiency of water. The goods after suitable scouring are entered and dyed with raising of temperature to a maximum preferably not above C. common salt being added as desired, according to the \Vhen this has been achieved on the two components the goods are Washed, dried and finished as requisite.

Example 7.

To dye a shade of lemon yellow on 25 kilogs. of woven fabriemade from cellulose acetate yarns 125grams of benzene-azophenylmethylpyrazolone are finely ground with 375 cc. of water and 500 grams of sulpho'aro- .matic'fatty acid preparation according to B.

above is added and whole stirred and heated to obtain maximum dispersion. It is then diluted with boili water and passed through asieve to the dye ath which may take the form of the jig type of machine. This dyebath should contain a sufficiency of water acidified with 250 grams of acetic acid The goods the temperature until the requisite shade is achieved when the usual rinsing and finishing processes as desired may follow. Example 8.

To print a shade of Tangerine oncellulose acetate woven fabric, the pa-ranitrobenzeneazodiphenylamine preparation cfitained according to Example 1, above is iluted, instead of with plain water, thickening of gum arabic and corn starch of suitable consistency for roller machine-print-' ing. The paste is acidified so as to contain 5' cc. per liter of 100% formic acid and is well.

boiled to give the highest degree of dispersion.

possible. After cooling it is applied in the usual manner in printing. The print is dried, aged for ,15 min. in dry steam and is then well washed, dried and finished as desired.

- What I claim and desire to secure by Letters Patent is: i

1. A process for the dyeing of materials are worked through the bath, raising with an aqueous comprising cellulose acetate which comprises treating said materials with relativelywater insoluble organic compounds capable of coloring cellulose ,acetate, said organic com- 3. A process for the dyeing of materials comprising cellulose-acetate which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic.-compounds'being. employed in th'eQform' of sol nbilized modifications obtained lgy pretreatng them with-a solubilizing agent compris mga salt'of sulphonaphth'alene stearic acid.

- 4. A process for the dyeing of materials comprising cellulose acetate which comprises treatin said materials with relatively water insoluble organic compounds capable of colcapable of coloring cellulose acetate,

- stearic acid.

oring celhzlose-lacetate, said organic compounds being, employed in the form of sol-. ubilized modifications obtained by p etreating them with a 's'olubilizing agent comprising sodium salt of sulphonaphthalene stearic acid.

,5.A 'pro'c ess for the dyeing of materials comprising cellulose acetate which comprises treatingsaid materials with relatively water a insoluble organic compounds of the azo class.

capable of x :oloi 'ing cellulose acetate, said organic form of solubilize'd modifications obtained by pretreating them with a solubilizing agentv comprisingv a itchell reagent.

6. A rocess for the dyeing otmaterials comprising'cellulose acetate which comprises treat-ing said materials withrel'atively water insoluble organic compounds of the azo class capable ofvacoloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by:

pretreating them with a solubilizing. agent comprising a sulphonaphthalene stearic acid,

body. I

7. A process for, the dyeing of materials comprising cellulose acetate which comprises treating said materials with relatively water insoluble organic compounds of the azo alas-(i $211 organic compbunds being employed'in the form of solubilized modifications obtained by pretreating them with' a solubilizing agent comprising a salt of sulphonaphthalene 8. A process for the comprising cellulose acetate w dyein of materials chcomprises treatingsaid materials with relativelywaterinsoluble organic compounds of the azo class compounds being employed in the capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comp-rising sodium salt of sulphonaphthalene stearic acid. I

.9. A 'process for the dyeing of materials comprising celluloseacetate which comprises treating'said materials with paranitrobenzene azo diphenylamine in the form ofa solubilized modification obtained by pretreat- Twitdhell reagent.

10. .A- process for the dyeing of materials comprising'cellulo'se acetate which comprises treating said materials with paranitrobenzene azo diphenylamine in the form of a solubilized modification obtained by pretreating ing itwith a solubilizing agent comprising a it with a solubilizing agent comprising a sulphonaplithalene stearic acid body.

11. A process for thedyeing of materials comprising cellulose acetate which comprises it with a solubilizing agent comprising a salt of sulphonaphthalene stearic acld.

- 12. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with paranitroben- 'zene azo diphenylamine in the form of a solubilized modification obtained by pretreating it with a 'solubilizing agent comprising sodium salt ofsulphonaphthalene stearic acid.

13. A process for the dyeing of mixedmaterials comprising cellulose acetate and other fibre which comprises treatin said materials with relatively water insolub e organic compounds capable of coloring cellulose acetate,

said organic compoundsbeing employed 1n the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a Twitchell reagent.

14. A processfor the dyeing-of mixed materials comprising cellulose acetate and other fibre which comprises treating said materials with relatively water insoluble organic compounds capable ofcoloring cellulose acetate, saidv organic compounds being employed in the form of solubilized 1 modifications obtained by pretreatingthem with a solubilizing agent comprising a sulphonaphthalene stearic acid body.,

15. A process for the dyeing of mixed materials comprising cellulose acetateand other fibre which comprises treating said materials with relatively water insoluble organic comsaid organic the form of solubilized modifications obtained by pretreating them with a solubiliz'ing agenttreating said materials with paranitrobenzene azo diphenylamine in the form of asolubilized modification obtained by pretreating pounds capable of coloring cellulose acetate, compounds being employed, in

comprising a salt of 'sulphonaphthalene f stearic acid.

16. A process for-the dyeing o f'mixed materials comprising cellulose acetateand other fibre which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained of solubilized modifications obtained by pre treating'them with a solubilizing agentcomprising a Twitchell reagent.

18. A process for the dyeingoi mixed materlals comprising cellulose'acetate and other fibre whlch comprises treating said materials 'with dyestuffs capable of coloringthe other fibre and with relatively water insolubleorganic compounds capable of coloring cellulose acetate, said relatively water insoluble organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a sulphonapthalene stearic acid body.-

19. A process for the dyeing of mixed materials comprising cellulose acetate and other fibre which comprises treating said materials with dyestuffs capable of coloring the other fibre and with relatively water insoluble organic compounds capable of coloring cellulose acetate, said relatively water insoluble organic compounds being employed in the form of solubilized modificationsobtainedby pretreating them with a solubilizing agent compricsling a salt of -sulphonaphthalene stearic ac] 20. A process for the dyeing of mixed materials, comprisingcellulose acetate and other fibre which comprises treating saidmaterials .with dyestuffs capable of coloring the other fibre and with relatively water insoluble orgame acetate, said relatively water-insoluble orgame of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphonaphthalene stearic acid. V

21. A process for the dyeing of mixed materials comprising cellulose acetate and wool which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a-solubilizing agent comprising a Twitchell reagent.

22. A process for the dyeing of mixed materials comprisingcellulose acetate and Wool compounds capable of cdloring cellulosecompoundsbeing employed in the form which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent oomprising a sulphonaphthalene stearic acid body. V Y

23. A process for the dyeing of mixed ma: terials comprising cellulose acetate andwool which comprises treating said materials with relatively water insoluble organic compounds wool which comprises treating said materials with relatively water insoluble organic compounds capable of coloring cellulose acetate, said organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphonapthalene stearic acid.

25. A process for the dyeing of mixed materials comprising cellulose acetate and wool which comprises treating said materials with dyestuffs capable of coloring wool, and with relatively water insoluble organic compounds capable of coloring cellulose acetate, said relatively water insoluble organic compounds being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising -a Twitchell reagent. 1

26. A process for the dyeing of mixed materials comprising cellulose acetate and wool which comprises treating said materials with dyestufi's capable of coloringwool, and with relatively water insoluble organic compounds capable of coloring celluloseacetate,v said relatively water. insoluble organic com ounds being employed in the form of solu ilized modifications obtained by prctreating them with a solubilizing agent comprising a sulphonapthalene stearic acid body,

2'7, A process for the dyeing of mixed materials comprising cellulose acetate and wool which comprises treating said materials with dyestuffs capable of coloring wool, and with relatively water insoluble organic compounds 1'20 capable of coloring cellulose acetate, said relatively water insoluble organic compounds being employed in the form of solubilized. modifications obtained by pretreating them with a solubilizing agent comprising a salt 125 of sulphonaphthalene stearic acid.

28. A process for the dyeing of mixed materials comprising cellulose acetate and wool which comprises treating said materials with dyestuffs capablecof coloring wool, and with '130 relatively waterinsoluble organic compounds 7 modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphonapthalene stearic acid.

29. A composition of matter applicable for the dyeing of cellulose acetate, comprising a solubilized modification of a relatively water insoluble organic compound capable of coloring cellulose acetate, said solubilized modification comprising a Twitchell reagent asa solubilizing agent.

30. A composition of matter applicable for the dyeing of cellulose acetate comprising a solubilized modification of a relatively Water insoluble organic compound capable of coloring cellulose acetate, said solubili zed modification comprising a sulphonapthalene stearicacid body as a solubilizing agent.

31. A composition of matter applicable for the dyeing of celiu'lose acetate, comprising a solubilized modification of a relatively water insoluble organic compound capable of coloring cellulose acetate, said solubilized modification comprising sodium salt of sulphonapthal ene' stearic acid as a solubilizing agent. 1

In testimony whereof I have hereunto subscribed my name, K,

" GEORGE HOLLAND ELLIS. 

